KR101728820B1 - Positive photosensitive resin composition, photosensitive resin film prepared by using the same, and display device - Google Patents

Abstract

(A) an alkali-soluble resin; (B) a photosensitive diazoquinone compound; (C) a phenol compound; (D) a thermal acid generator; And (E) a solvent, wherein the solvent comprises an organic solvent having a boiling point of less than 160 ° C. and an organic solvent having a boiling point of 160 ° C. or higher at atmospheric pressure, and the organic solvent having a boiling point of less than 160 ° C., Wherein the organic solvent having a boiling point of 160 DEG C or higher is contained in an amount of more than 0 wt% to 10 wt% with respect to the total amount of the solvent, and a photosensitive resin Film, and display element are provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a positive photosensitive resin composition, a photosensitive resin film, and a display element,

The present invention relates to a positive photosensitive resin composition, a photosensitive resin film produced using the positive photosensitive resin composition, and a display element comprising the photosensitive resin film.

BACKGROUND ART [0002] Heat resistant resins such as polyimide and polybenzoxazole are widely used as an interlayer insulating film or a planarizing film of an organic EL device, a display device such as an LCD, or the like. In recent years, in order to form an interlayer insulating film of an organic light emitting device, a heat-resistant photosensitive polyimide and a photosensitive polybenzoxazole are widely used for securing reliability of an OLED device. Photosensitive polyimide and polybenzoxazole are excellent in physical properties such as heat resistance and mechanical strength and have excellent electric characteristics such as low dielectric constant and high insulation and also have a good planarization property of the coating surface and a content of impurities It is very low, and it is advantageous to easily make a fine shape.

On the other hand, when the heat-resistant resin is used for an insulating film or a planarizing film of an organic EL device, the size of the substrate to which the photosensitive resin composition is applied is very large as compared with the application to the semiconductor, . The method of applying the composition to the insulating film or the planarizing film of the organic EL element generally adopts a method of applying the resin composition by slit coating. The slit coating is a coating method using a slit nozzle and can be applied to a large-sized substrate. Unlike conventional spin coating, since it is not necessary to rotate the substrate, the use amount of the resin composition can be reduced and applied to a display device manufacturing process . Since the coating film applied when the coating liquid discharged from the slit nozzle is applied to the substrate during the slit coating process contains a large amount of solvent, the solvent is removed by drying under reduced pressure at room temperature after the coating, and then heated Drying is common.

Therefore, it is important to select a solvent suitable for slit coating in a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor and a photosensitizer used in an insulating film, a planarizing film, and the like in the production of an organic EL device.

One embodiment is to provide a positive photosensitive resin composition excellent in residual film ratio and sensitivity.

Another embodiment is to provide a photosensitive resin film using the above positive photosensitive resin composition.

Another embodiment is to provide a display element comprising the photosensitive resin film.

One embodiment includes (A) an alkali soluble resin; (B) a photosensitive diazoquinone compound; (C) a phenol compound; (D) a thermal acid generator; And (E) a solvent, wherein the solvent comprises an organic solvent having a boiling point of less than 160 ° C. and an organic solvent having a boiling point of 160 ° C. or higher at atmospheric pressure, and the organic solvent having a boiling point of less than 160 ° C., To 90% by weight or more and less than 100% by weight based on the total amount of the solvent, and the organic solvent having a boiling point of 160 ° C or more is contained in an amount of more than 0 wt% to 10 wt% or less based on the total amount of the solvent.

The solvent may be an organic solvent having a boiling point of less than 160 ° C and an organic solvent having a boiling point of 160 ° C or higher at a ratio of 90:10 to 99.5: 0.5 under atmospheric pressure.

The solvent may be an organic solvent having a boiling point of less than 160 DEG C and an organic solvent having a boiling point of 160 DEG C or higher at a ratio of 90:10 to 95: 5 under atmospheric pressure.

The solvent may include an organic solvent having a boiling point of at least 100 ° C and less than 160 ° C at atmospheric pressure and an organic solvent having a boiling point of 160 ° C or more and less than 280 ° C.

The alkali-soluble resin may be a polybenzoxazole precursor, a polyimide precursor, or a combination thereof.

The polybenzoxazole precursor includes a structural unit represented by the following formula (1), and the polyimide precursor may include a structural unit represented by the following formula (2).

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

X ¹ is a substituted or unsubstituted C6 to C30 aromatic organic group,

X ² is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic group, ,

Y ¹ is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic group- ego,

Y ² is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted quadrivalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted quadrivalent to hexavalent C3 to C30 alicyclic group- to be.

Wherein the positive photosensitive resin composition comprises 5 to 100 parts by weight of the photosensitive diazoquinone compound (B) per 100 parts by weight of the alkali-soluble resin (A); 1 to 30 parts by weight of the phenol compound (C); (D) 1 to 50 parts by weight of a thermal acid generator; And 100 to 2000 parts by weight of the above (E) solvent.

The positive photosensitive resin composition may further include an additive selected from the group consisting of a surfactant, a leveling agent, a silane coupling agent, and a combination thereof.

Another embodiment provides a photosensitive resin film produced using the positive photosensitive resin composition.

Another embodiment provides a display element comprising the photosensitive resin film.

The positive-working photosensitive resin composition according to one embodiment can provide a photosensitive resin film having excellent residual film ratio and sensitivity, and a display device.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Means that at least one hydrogen atom of the functional group of the present invention is substituted with a halogen atom (F, Br, Cl or I), a hydroxyl group, a nitro group, a cyano group, an amino group NH _2, NH (R ^200), or N (R ²⁰¹⁾ (R ^202), wherein R ^200, R ²⁰¹ and R ²⁰² are the same or different, each independently being a C1 to C10 alkyl groups), amidino group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, And a substituted or unsubstituted heterocyclic group substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Means a C1 to C20 alkyl group, specifically, a C1 to C15 alkyl group, and the "cycloalkyl group" means a C3 to C20 cycloalkyl group, and specifically, C3 Refers to a C1 to C20 alkoxy group, specifically, a C1 to C18 alkoxy group, and the "aryl group" means a C6 to C20 aryl group, specifically, a C6 to C20 aryl group, Refers to a C 2 to C 20 alkenyl group, specifically, a C 2 to C 18 alkenyl group, and the "alkylene group" refers to a C 1 to C 20 alkylene group, specifically, a C1 Refers to a C6 to C20 arylene group, and specifically refers to a C6 to C16 arylene group.

Unless otherwise specified in the present specification, the term "aliphatic organic group" means a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 alkylene group, a C2 to C20 alkenylene group, Means a C1 to C15 alkyl group, a C2 to C15 alkenyl group, a C2 to C15 alkynyl group, a C1 to C15 alkylene group, a C2 to C15 alkenylene group, or a C2 to C15 alkynylene group, Means a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C3 to C20 cycloalkylene group, a C3 to C20 cycloalkenylene group, or a C3 to C20 cycloalkynylene group. And more specifically a C3 to C15 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C3 to C15 cycloalkynyl group, a C3 to C15 cycloalkylene group, a C3 to C15 cycloalkenylene group, or a C3 to C15 cyclo Means a C6 to C20 aryl group or a C6 to C20 arylene group, specifically a C6 to C16 aryl group or a C6 to C16 arylene group, and the "heterocyclic group" Means a C2 to C20 cycloalkyl group, a C2 to C20 cycloalkylene group, a C2 to C20 cycloalkylene group, a C2 to C20 cycloalkylene group, a C2 to C20 cycloalkylene group, a C2 to C20 cycloalkylene group, A C2 to C20 cycloalkynylene group, a C2 to C20 cycloalkynylene group, a C2 to C20 heteroaryl group, or a C2 to C20 heteroarylene group, and specific examples include O, A C 2 to C 15 cycloalkyl group, a C 2 to C 15 cycloalkylene group, a C 2 to C 15 cycloalkenyl group having 1 to 3 hetero atoms selected from the group consisting of S, N, P, Si and combinations thereof in one ring, , A C2 to C15 cycloalkenylene group, a C2 to C15 cycloalkynyl group, a C2 to C15 cycloalkynylene group, a C2 to C15 heteroaryl group, or a C2 to C15 heteroarylene group.

As used herein, unless otherwise defined, "combination" means mixing or copolymerization. "Copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the present specification, "*" means the same or different atom or part connected to a chemical formula.

One embodiment includes (A) an alkali soluble resin; (B) a photosensitive diazoquinone compound; (C) a phenol compound; (D) a thermal acid generator; And (E) a solvent, wherein the solvent comprises an organic solvent having a boiling point of less than 160 ° C. and an organic solvent having a boiling point of 160 ° C. or higher at atmospheric pressure, and the organic solvent having a boiling point of less than 160 ° C., To 90% by weight or more and less than 100% by weight based on the total amount of the solvent, and the organic solvent having a boiling point of 160 ° C or more is contained in an amount of more than 0 wt% to 10 wt% or less based on the total amount of the solvent.

The positive photosensitive resin composition according to one embodiment contains an organic solvent in which a low boiling point solvent having a boiling point of less than 160 DEG C at atmospheric pressure and a high boiling point solvent having a boiling point of not less than 160 DEG C at atmospheric pressure are mixed in an appropriate ratio, The residual photosensitive film and the sensitivity are excellent.

The boiling point of the organic solvent at atmospheric pressure is described in the literature such as " Aldrich Handbook of Fine Chemical and Laboratory Equipment ", and the boiling point of the organic solvent not described in the known literature is commercially available boiling point measuring apparatus such as FP81HT / FP81C (Mettler Toledo International Inc.).

Each component will be described in detail below.

(E) Solvent

The positive-working photosensitive resin composition according to one embodiment includes a solvent capable of easily dissolving each component to be described later, for example, an alkali-soluble resin or the like.

As described above, since the photosensitive resin composition used for the insulating film, the planarizing film, and the like of the organic EL element is applied on the substrate having a large area, the application can be performed by the slit coating method. In this case, when the solvent used in the composition is a high-boiling solvent, there is a problem that the unexposed area is easily washed out and the residual film ratio is lowered in the development, so a low boiling solvent is generally used. In case of a low boiling solvent, have.

However, in the composition according to one embodiment, the low boiling point solvent and the high boiling point solvent are mixed in an appropriate ratio, for example, 90:10 to 99.5: 0.5 or 90:10 to 95: 5, The residual film ratio of the unexposed portion can be increased.

The solvent is preferably used in an amount of 100 to 2000 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the solvent is within the above range, it is possible to coat a film having a sufficient thickness, and it is excellent in residual film ratio, sensitivity, solubility and coating property.

(E-1) An organic solvent having a boiling point lower than 160 占 폚

The composition according to one embodiment is a low boiling point solvent, which is an organic solvent having a boiling point of less than 160 占 폚 at atmospheric pressure of not less than 90% by weight, such as not less than 90% by weight and not more than 100% by weight, for example, not less than 95% .

When the content of the organic solvent having a boiling point of less than 160 캜 under atmospheric pressure is out of the above range, the solvent having a high boiling point is increased during drying under reduced pressure after slit coating, and the high boiling point solvent does not escape well and remains in the coating film, The unexposed area is easily washed away and the residual film ratio is lowered.

Further, when a high boiling point solvent remains in the reduced pressure drying after the slit coating, a high boiling point solvent excellent in interaction with the alkali soluble resin surrounds the alkali soluble resin, so that the mutual interaction between the alkali soluble resin and the photosensitive diazoquinone compound Thereby weakening the action. That is, the high-boiling solvent not only strongly interacts with the alkali-soluble resin but also strongly interacts with the photosensitive diazoquinone compound, so that the bond between the alkali-soluble resin and the photosensitive diazoquinone compound is not well established, The residual film ratio of the unexposed portion is lowered, and the developability of the aqueous alkali solution is lowered in the exposed portion, resulting in poor sensitivity.

When the content of a solvent having a boiling point of 160 캜 or more under a high boiling point solvent, that is, at atmospheric pressure is increased, the residual film ratio and sensitivity become worse.

The organic solvent having a boiling point of less than 160 캜 under atmospheric pressure may be an organic solvent having a boiling point of at least 100 캜 and less than 160 캜 under atmospheric pressure.

It is preferable that an organic solvent having a boiling point of less than 160 占 폚 at atmospheric pressure, for example, an organic solvent having a boiling point of 100 占 폚 or more and less than 160 占 폚 under atmospheric pressure is capable of dissolving the alkali-soluble resin. Examples thereof include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether (boiling point 124 ° C) and propylene glycol monomethyl ether (boiling point 118 ° C), propyl acetate (boiling point 102 (Boiling point: 122 占 폚), methyl butyl ketone (boiling point: 120 占 폚), and the like; alkyl acetates such as butyl acetate (boiling point: 125 占 폚) and isobutyl acetate Ketones such as ketone such as methyl isobutyl ketone (boiling point 116 占 폚) and cyclopentanone (boiling point 130.6 占 폚), n-butyl alcohol (boiling point 117 ° C), isobutyl alcohol (boiling point 108 ° C), isobutyl alcohol (boiling point 108 ° C), ethyl lactate (boiling point 155 ° C), pentan-1-ol (Boiling point 138.5 ° C), 3-Methylbutan-1-ol (boiling point 131.2 ° C), 4-methyl (methylphenol) (Boiling point: 131.6 ° C), aromatic hydrocarbons such as toluene and xylene, N, N-dimethyl formamide (boiling point: 153 ° C) and the like .

(E-2) An organic solvent having a boiling point of 160 占 폚 or higher

The composition according to one embodiment is a high boiling point solvent which is an organic solvent having a boiling point of 160 ° C or higher at atmospheric pressure of 10 wt% or less, for example, 0 wt% or more and 10 wt% or less, for example, 0.5 wt% or more and 10 wt% or less , For example, 5 wt% or more and 10 wt% or less.

When an organic solvent having a boiling point of 160 ° C or higher is used within a range of the above range under a high boiling solvent such as atmospheric pressure, the uniformity of the film of the photosensitive resin film is increased and the penetration of the alkali developing solution is suppressed in the non- The acid generation of the quinone compound facilitates the penetration of the alkali developer.

The use of a high boiling point solvent having low compatibility with the alkali soluble resin in the high boiling point solvent suppresses the reduction of the residual film at the time of development and improves the sensitivity. As described above, when the alkali-soluble resin is too soluble in the solvent and the compatibility between the high-boiling solvent and the alkali-soluble resin is too good, the interaction between the alkali-soluble resin and the photosensitive diazoquinone compound is reduced, And the alkali developing solution can not easily penetrate due to the high boiling point solvent surrounding the alkali-soluble resin in the exposed part, so that the scum and the pattern are likely to be uneven.

The organic solvent having a boiling point of 160 ° C or higher under atmospheric pressure can be an organic solvent having a boiling point of 160 ° C or more and less than 300 ° C under atmospheric pressure.

An organic solvent having a boiling point of 160 ° C or higher at atmospheric pressure, for example, an organic solvent having a boiling point of 160 ° C or more and less than 300 ° C under atmospheric pressure is preferably capable of dissolving the alkali-soluble resin. For example, N, N-dimethyl acetamide (boiling point 165 ° C), diacetone alcohol (boiling point 166 ° C), butyl lactate (boiling point 170 ° C) N-Methyl-2-pyrrolidone (boiling point: 204 DEG C), diethyleneglycol ethylmethyl ether (boiling point 179 DEG C), dimethyl sulfoxide (boiling point 189 DEG C) Diphenyl ether (boiling point 258 占 폚), N-cyclohexyl-2-pyrrolidone (boiling point 284 占 폚), and the like.

(A) an alkali-soluble resin

The alkali-soluble resin may be a polybenzoxazole precursor, a polyimide precursor, or a combination thereof. For example, the alkali-soluble resin may be a polybenzoxazole precursor.

The polybenzoxazole precursor may include a structural unit represented by the following formula (1), and the polyimide precursor may include a structural unit represented by the following formula (2).

[Chemical Formula 1]

In Formula 1,

X < ¹ > may be a substituted or unsubstituted C6 to C30 aromatic organic group,

Y ¹ is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group .

(2)

In Formula 2,

X ² is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group However,

Y ² is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted quadrivalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted quadrivalent to hexavalent C3 to C30 alicyclic organic group .

In the above formula (1), X ¹ is an aromatic organic group and may be a residue derived from an aromatic diamine.

Examples of the aromatic diamine include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2- Hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2- (3-amino-4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis , 2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2- rope (4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis Phenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- 2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- 2- (3-amino-4-amino-6-trifluoromethylphenyl) hexafluoropropane, 2- 2-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-2-trifluoromethylphenyl) Methylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane and 2- Hydroxy-6-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane may be used, It is not.

Examples of X ¹ include functional groups represented by the following formulas (3) and (4), but are not limited thereto.

(3)

[Chemical Formula 4]

In the above formulas (3) and (4)

A ¹ may be a single bond, O, CO, CR ⁴⁷ R ⁴⁸ , SO ₂ or S, and R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, May be a C1 to C30 fluoroalkyl group,

Each of R ⁵⁰ to R ⁵² independently represents a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxyl group or a thiol group,

n10 may be an integer of 0 to 2, and n11 and n12 may be an integer of 0 to 3, respectively.

In formula (1), Y ¹ is an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic group, and may be a residue of a dicarboxylic acid or a residue of a dicarboxylic acid derivative. Specifically, Y ¹ may be an aromatic organic group, or a divalent to hexavalent alicyclic organic group.

Specific examples of the dicarboxylic acid derivative include 4,4'-oxydibenzoyl chloride, diphenyloxydicarbonyldichloride, bis (phenylcarbonyl chloride) sulfone, bis (phenylcarbonyl chloride) ether, bis (phenylcarbonyl chloride ) Phenone, phthaloyldichloride, terephthaloyldichloride, isophthaloyldichloride, dicarbonyldichloride, diphenyloxydicarboxylate dibenzotriazole, or combinations thereof, but is not limited thereto.

Examples of Y ¹ include functional groups represented by the following formulas (5) to (7), but are not limited thereto.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 5 to 7,

Each of R ⁵³ to R ⁵⁶ may independently be a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group,

n13 and n14 may each be an integer of 0 to 4, n15 and n16 may each be an integer of 0 to 3,

A ² may be a single bond, O, CR ⁴⁷ R ⁴⁸ , CO, CONH, S or SO ₂ , and R ⁴⁷ and R ⁴⁸ each independently may be a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group , Specifically a C1 to C30 fluoroalkyl group.

In Formula 2, X ² is an aromatic organic group, a divalent to hexavalent aliphatic organic group, and a divalent to hexavalent alicyclic organic group. Specifically, X ² may be an aromatic organic group or a divalent to hexavalent alicyclic organic group.

Specifically, X ² may be a residue derived from an aromatic diamine, an alicyclic diamine or a silicone diamine. At this time, the aromatic diamine, alicyclic diamine and silicon diamine may be used singly or in combination of one or more thereof.

Examples of the aromatic diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine , Bis [4- (4-aminophenoxy) phenyl] sulfone, bis (4-aminophenoxy) ] Ether, 1,4-bis (4-aminophenoxy) benzene, a compound in which the aromatic ring thereof is substituted with an alkyl group or a halogen atom, or a combination thereof, but is not limited thereto.

Examples of the alicyclic diamine include, but are not limited to, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, or a combination thereof.

Examples of the silicon diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p- aminophenyl) tetramethyldisiloxane, Bis (? -Aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (? -Aminopropyl) tetraphenyldisiloxane, 1,3- Methyldisiloxane, or combinations thereof, but are not limited thereto.

In the above formula (2), Y ² is an aromatic organic group, an aliphatic organic group having from 4 to 6 aliphatic organic groups, or a aliphatic organic group having from 4 to 6 aliphatic groups. Specifically, Y ² may be an aromatic organic group, or a divalent to hexavalent alicyclic organic group.

The Y ² may be an aromatic acid dianhydride, or a residue derived from an alicyclic acid dianhydride. At this time, the aromatic acid dianhydride and the alicyclic acid dianhydride may be used alone or in admixture of at least one thereof.

Examples of the aromatic acid dianhydride include pyromellitic dianhydride; Benzophenone tetracarboxylic dianhydride such as benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3'4,4'-tetracarboxylic dianhydride, ; Oxydiphthalic dianhydride such as 4,4'-oxydiphthalic dianhydride; Biphthalic dianhydride such as 3,3 ', 4,4'-biphthalic dianhydride (3,3', 4,4'-biphthalic dianhydride); (Hexafluoroisopropylidene) diphthalic dianhydride such as 4,4 '- (hexafluoroisopropylidene) diphthalic dianhydride (4,4' - (hexafluoroisopropylidene) diphthalic dianhydride) ; Naphthalene-1,4,5,8-tetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic dianhydride, and the like, but the present invention is not limited thereto.

Examples of the alicyclic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1,2-dicarboxylic acid dianhydride (5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1,2-dicarboxylic anhydride), 4- (2,5- dioxotetrahydrofuran-3-yl) -tetralin- (2,5-dioxotetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic anhydride, bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5,6-tetracarboxylic dianhydride, bicyclooctene-1,2,4,5-tetracarboxylic dianhydride, and the like. But is not limited thereto.

The alkali-soluble resin has a thermally polymerizable functional group derived from a reactive terminal blocking monomer on one or both of the branched chain terminals. The reactive end blocking monomer is preferably a monoamine having a carbon-carbon double bond or a monoanhydride, or a combination thereof. Examples of the monoamines include, but are not limited to, toluidine, dimethyl aniline, ethyl aniline, aminophenol, aminobenzyl alcohol, aminoindan, aminoacetone phenone, and combinations thereof.

The alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 to 300,000 g / mol. When the weight average molecular weight is within the above range, sufficient physical properties can be obtained and the solubility in an organic solvent is excellent and handling is easy.

(B) Photosensitive Diazoquinone  compound

As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure can be preferably used.

Representative examples of the photosensitive diazoquinone compound include compounds represented by the following general formulas (17) and (19) to (21), but are not limited thereto.

[Chemical Formula 17]

In Formula 17,

R ₃₁ to R ₃₃ are each independently hydrogen or a substituted or unsubstituted alkyl group, for example, CH ₃ ,

D ₁ to D ₃ are each independently OQ and Q may be hydrogen or the following formula 18a or 18b wherein Q can not be hydrogen at the same time,

n31 to n33 each independently represents an integer of 1 to 3;

[Formula 18a]

[Formula 18b]

[Chemical Formula 19]

In the above formula (19)

R ₃₄ is hydrogen or a substituted or unsubstituted alkyl group,

D ₄ to D ₆ are OQ, Q is the same as defined in Formula 17,

n34 to n36 each independently represent an integer of 1 to 3;

[Chemical Formula 20]

In the above formula (20)

A ₃ is CO or CRR ', R and R' are each independently a substituted or unsubstituted alkyl group,

D ₇ to D ₁₀ are the same as the one, each independently, hydrogen, substituted or unsubstituted alkyl, OQ, or NHQ ring, wherein Q is as defined in Formula 17,

n37, n38, n39 and n40 are each independently an integer of 1 to 4,

n37 + n38 and n39 + n40 are each independently an integer of 5 or less,

Provided that at least one of the D ₇ to D ₁₀ are OQ, one aromatic ring has an OQ can contain 1 to 3, there is OQ can contain one to four and one of the aromatic ring.

[Chemical Formula 21]

In Formula 21,

R ₃₅ to R ₄₂ are each independently hydrogen or a substituted or unsubstituted alkyl group,

n41 and n42 are each independently an integer of 1 to 5, for example, an integer of 2 to 4,

Q is the same as defined in Formula 17 above.

The photosensitive diazoquinone compound is preferably included in an amount of 5 to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the photosensitive diazoquinone compound is within the above range, the pattern is formed well without residue by exposure, and a good pattern can be obtained without loss of film thickness upon development.

(C) Phenol compound

The phenolic compound increases the dissolution rate and sensitivity of the exposed portion during development with an alkaline aqueous solution, and helps to pattern at a high resolution.

Representative examples of such phenol compounds include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl- However, the present invention is not limited thereto.

Representative examples of the phenol compound include, but are not limited to, those represented by the following formulas (25) to (30).

(25)

In Formula 25,

R ₉₁ to R ₉₃ may be the same or different from each other, and each independently hydrogen, or a substituted or unsubstituted alkyl group,

R ₉₄ to R ₉₈ may be the same or different and each independently H, OH, or a substituted or unsubstituted alkyl group, preferably the alkyl group may be CH ₃ ,

n91 may be an integer of 1 to 5.

(26)

In Formula 26,

R ₉₉ to R ₁₀₄ are the same or different and are each independently H, OH, or a substituted or unsubstituted alkyl group,

A ₄ may be CR'R "or a single bond, and R 'and R" may be the same or different and each independently hydrogen, or a substituted or unsubstituted alkyl group, may be CH _3,

n92 + n93 + n94 and n95 + n96 + n97 may be the same or different from each other and independently of each other may be an integer of 5 or less.

(27)

In Formula 27,

R ₁₀₅ to R _{107, which} may be the same or different from each other, are each independently hydrogen or a substituted or unsubstituted alkyl group,

n98, n99 and n102 may be the same or different from each other and each independently an integer of 1 to 5,

n100 and n101 may be the same or different from each other and each independently an integer of 0 to 4;

(28)

In Formula 28,

R ₁₀₈ to R ₁₁₃ are the same or different from each other and are each independently hydrogen, OH, or a substituted or unsubstituted alkyl group,

n103 to n106 may be the same or different from each other and each independently may be an integer of from 1 to 4,

Here, n103 + n105 and n104 + n106 are each independently an integer of 5 or less.

[Chemical Formula 29]

In the above formula (29)

R ₁₁₄ may be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₁₁₅ to R ₁₁₇ may be the same or different from each other and each independently hydrogen, or a substituted or unsubstituted alkyl group,

n107, n109 and n111 may be the same or different from each other and each independently an integer of 1 to 5,

n108, n110 and n112 may be the same or different from each other and each independently an integer of 0 to 4,

However, n107 + n108, n109 + n110, and n111 + n112 are each independently an integer of 5 or less.

(30)

In Formula 30,

R ₁₁₈ to R ₁₂₀ may be the same or different from each other, and each independently may be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₁₂₁ to R ₁₂₄ may be the same or different from each other and each independently hydrogen or a substituted or unsubstituted alkyl group,

n113, n115 and n118 may be the same or different from each other, and each independently may be an integer of 1 to 5,

n114, n116 and n117 may be the same or different from each other, and each independently may be an integer of 0 to 4,

n119 may be an integer of 1 to 4,

Here, n113 + n114, n115 + n116 and n117 + n118 are each independently an integer of 5 or less.

The phenolic compound is preferably used in an amount of about 1 to about 30 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the phenolic compound is within the above range, the dissolution rate and sensitivity of the exposed portion can be increased upon development with an alkaline aqueous solution, and the resist pattern can be patterned at high resolution without development residue (scum) at the time of development.

(D) Thermal acid Generator

The thermal acid generators used in the present invention are those capable of decomposing by heat and capable of generating an acid, and can use ordinary thermal acid generators. Preferably, the thermal acid generators can be decomposed by heat (thermal decomposition temperature) Can be used.

When a thermal acid generator having a pyrolysis temperature within the above range is used, an outgas reduction effect and excellent reliability can be exhibited.

As the thermal acid generator used in the present invention, for example, compounds represented by the following Chemical Formulas 36, 37, or a combination thereof can be used.

(36)

(37)

In Formula 36 and 37, R ¹ is a hydrogen atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, R ² is a hydrogen atom, a substituted or unsubstituted hwandoen a C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, or a combination thereof, R ³ is a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl , a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, R ⁴ is a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, or a combination thereof, R ⁵ is a hydrogen atom, a halogen atom, a substituted Or an unsubstituted C1 to C30 alkyl group, or a combination thereof,

The formula (36) may be represented by any one selected from the group consisting of the following formulas (36a) to (36c).

[Chemical Formula 36a]

(36b)

[Chemical Formula 36c]

M1 to m4 are each independently an integer of 0 to 10, preferably 0 to 6; and Z ₁ to Z ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, .

The above formulas (36) and (37) may be represented by the following formulas (38) to (44).

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

The compounds represented by the following formulas (45) to (48) may also be used as a thermal acid generator.

[Chemical Formula 45]

(46)

(47)

(48)

The content of the thermal acid generator is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the polybenzoxazole precursor. When the content of the thermal acid generators is in the above range, the polybenzoxazole precursor is sufficiently cycled so that the prepared insulating film can have excellent thermal and mechanical properties, and the composition can have excellent storage stability.

The thermal acid generators may be selected according to the curing temperature conditions, and may be used alone or in combination of two or more.

In addition to the thermal acid generators, allylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and fluorobutanesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid may be used.

(F) Other additives

The positive photosensitive resin composition according to one embodiment may further include other additives.

As other additives, a suitable surfactant or leveling agent may be used to prevent unevenness in film thickness or to improve developability. Also, a silane coupling agent may be used as an adhesion promoting agent for enhancing adhesion to a substrate.

The surfactant, leveling agent, and silane coupling agent may be used alone or in combination.

The surfactant may include a siloxane surfactant or a surfactant having a fluorine atom, and the surfactant may be included in an amount of 0.005 parts by weight or more and 0.3 parts by weight or less based on 100 parts by weight of the photosensitive resin composition. When the surfactant is used within the above range, the occurrence of stains is minimized and the uniformity of the film is improved.

Examples of the siloxane-based surfactant include BYK series manufactured by BYK, Germany. Examples of the surfactant having a fluorine atom include Mega Face series manufactured by Dainippon Ink and Chemicals, Inc., but are not limited thereto.

The step of forming a pattern using the positive photosensitive resin composition according to the embodiment may include a step of applying a positive photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing or the like; Drying the applied positive photosensitive resin composition to form a positive photosensitive resin composition film; Exposing the positive photosensitive resin composition film; A step of developing the exposed positive photosensitive resin composition film with an alkali aqueous solution to prepare a photosensitive resin film; And a step of heat-treating the photosensitive resin film. The process conditions for forming the pattern, and the like are well known in the related art, and therefore, a detailed description thereof will be omitted herein.

According to another embodiment of the present invention, there is provided a photosensitive resin film produced using the positive photosensitive resin composition according to the above embodiment.

The photosensitive resin film may be used as an organic insulating film, a buffer film, or a protective film.

According to another embodiment of the present invention, there is provided a display device comprising the photosensitive resin film.

Specifically, the display device may be an organic light emitting diode (OLED) or a liquid crystal display device (LCD).

That is, the positive photosensitive resin composition according to one embodiment of the present invention can be usefully used for forming an organic insulating film, a planarizing film, a passivation layer, an interlayer insulating layer, or the like in a display device.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are only the preferred embodiments of the present invention, and the present invention is not limited to the following Examples.

( Synthetic example )

Synthetic example  One: Polybenzoxazole  Precursor ( PA -1) Synthesis of

(3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-tetra-naphthalene-2-carboxylate was obtained by passing nitrogen through a four-necked flask equipped with a stirrer, a temperature controller, 3-hexafluoropropane, and 0.86 g of 1,3-bis (aminopropyl) tetramethyldisiloxane, and 280 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve. In the obtained solution, the solid content was 9% by weight.

When the solid was completely dissolved, 9.9 g of pyridine was added, and 13.3 g of 4,4'-oxydibenzoyl chloride was dissolved by adding 142 g of N-methyl-2-pyrrolidone (NMP) while maintaining the temperature at 0 to 5 ° C Was slowly added dropwise over 30 minutes. After the dropwise addition, the reaction was carried out at a temperature of 0 to 5 ° C for 1 hour, and then the temperature was raised to room temperature to carry out the reaction for 1 hour.

To this was added 1.6 g of 5-norbornene-2,3-dicarboxyanhydride and the mixture was stirred at room temperature for 2 hours to complete the reaction. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to produce a precipitate, and the precipitate was filtered and sufficiently washed with water. The polybenzoxazole precursor (PA-1) was prepared by drying at 80 캜 under vacuum for at least 24 hours.

Synthetic example  2: Polybenzoxazole  Precursor ( PA -2)

A polybenzoxazole precursor (PA-2) was prepared by polymerizing in the same manner as in Synthesis Example 3 except that maleic anhydride was used instead of 5-norbornene-2,3-dicarboxyanhydride.

Synthetic example  3: Polybenzoxazole  Precursor ( PA -3)

A polybenzoxazole precursor (PA-3) was prepared by polymerization in the same manner as in Synthesis Example 3 except that aconitic hydride was used instead of 5-norbornene-2,3-dicarboxyanhydride.

Preparation of positive photosensitive resin composition

[Example 1]

15 g of the polybenzoxazole precursor (PA-1) synthesized in Synthesis Example 1 was added and dissolved. Then, 5.31 g of photosensitive diazoquinone represented by the following Formula A, 3.75 g of a phenol compound represented by the following Formula B, Butyl acrylate (boiling point 205 占 폚), 6.160 g of ethyl lactate (boiling point 158 占 폚), 57.496 g of ethyl lactate (boiling point 158 占 폚), 6.160 g of? -Butyllactone 0.037 g of leveling agent F-554 was added and stirred, followed by filtration with a 0.45 占 퐉 fluorine resin filter to obtain a positive photosensitive resin composition.

(A)

로 표시되고, 나머지 하나는 수소원자이다.)(In the formula, Q ₁ to Q ₃ are two of the

And the other is a hydrogen atom.)

[Chemical Formula B]

(38)

[Example 2]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 1, except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Example 3]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 1, except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Example 4]

Except that the solvent composition of Example 1 was changed to 0 g of propylene glycol monomethyl ether (boiling point 118 占 폚), 195.076 g of ethyl lactate (boiling point 158 占 폚), and 10.267 g of? -Butyl lactone (boiling point 205 占 폚) A positive photosensitive resin composition was prepared.

[Example 5]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 4, except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Example 6]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 4, except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Example 7]

The solvent composition of Example 1 was changed to 102.672 g of propylene glycol monomethyl ether (boiling point 118 캜), 92.405 g of ethyl lactate (boiling point 158 캜) and 10.267 g of? -Butyl lactone (boiling point 205 캜) 1, a positive photosensitive resin composition was prepared.

[Example 8]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 4, except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Example 9]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 4, except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Example 10]

Except that the solvent composition of Example 1 was changed to 82.137 g of propylene glycol monomethyl ether (boiling point 118 DEG C), 112.939 g of ethyl lactate (boiling point 158 DEG C) and 10.267 g of diphenyl ether (boiling point 258 DEG C) A positive-type photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 11]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 10 except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 12]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 10 except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 13]

Except that the solvent composition of Example 10 was changed to 0 g of propylene glycol monomethyl ether (boiling point 118 占 폚), 195.076 g of ethyl lactate (boiling point 158 占 폚), and 10.267 g of diphenyl ether (boiling point 258 占 폚) A positive photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 14]

A positive photosensitive resin composition was prepared in the same manner as in Example 13 except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 15]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 13 except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 16]

Except that the solvent composition of Example 10 was changed to 102.672 g of propylene glycol monomethyl ether (boiling point 118 DEG C), 92.405 g of ethyl lactate (boiling point 158 DEG C) and 10.267 g of diphenyl ether (boiling point 258 DEG C) A positive-type photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 17]

A positive photosensitive resin composition was prepared in the same manner as in Example 16 except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 18]

A positive photosensitive resin composition was prepared in the same manner as in Example 16 except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 19]

Except that the solvent composition of Example 1 was changed to 130.12 g of methyl ethyl ketone (boiling point 79.6 캜), 52.93 g of ethyl lactate (boiling point 158 캜), and 9.45 g of dimethyl sulfoxide (boiling point 189 캜) A positive photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 20]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 19 except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 21]

A positive photosensitive resin composition was prepared in the same manner as in Example 19 except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 22]

The solvent composition of Example 1 was changed to 182.86 g of methyl ethyl ketone (boiling point 79.6 캜), 0 g of ethyl lactate (boiling point 158 캜), and 9.64 g of dimethyl sulfoxide (boiling point 189 캜) 1, a positive photosensitive resin composition was prepared.

[Example 23]

A positive photosensitive resin composition was prepared in the same manner as in Example 22 except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 24]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 22 except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 25]

Except that the solvent composition of Example 1 was changed to 96.24 g of methyl ethyl ketone (boiling point 79.6 占 폚), 86.62 g of ethyl lactate (boiling point 158 占 폚), and 9.64 g of dimethyl sulfoxide (boiling point 189 占 폚) A positive photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 26]

A positive photosensitive resin composition was prepared in the same manner as in Example 22 except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Example 27]

A positive-type photosensitive resin composition was prepared in the same manner as in Example 22 except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1).

[Comparative Example 1]

The solvent composition of Example 1 was changed to 134.65 g of propylene glycol monomethyl ether (boiling point 118 캜), 38.56 g of ethyl lactate (boiling point 158 캜) and 19.28 g of? -Butyl lactone (boiling point 205 캜) 1, a positive photosensitive resin composition was prepared.

[Comparative Example 2]

A positive-type photosensitive resin composition was prepared in the same manner as in Comparative Example 1, except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Comparative Example 3]

A positive photosensitive resin composition was prepared in the same manner as in Comparative Example 1 except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Comparative Example 4]

Except that the solvent composition of Example 1 was changed to 164.275 g of propylene glycol monomethyl ether (PGME, 118 캜), 0 g of ethyl lactate (EL, boiling point 158 캜) and 41.069 g of? -Butyl lactone (GBL, boiling point 205 캜) A positive-type photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 5]

A positive-type photosensitive resin composition was prepared in the same manner as in Comparative Example 4, except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Comparative Example 6]

A positive-type photosensitive resin composition was prepared in the same manner as in Comparative Example 4, except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Comparative Example 7]

The solvent composition of Example 1 was changed to 143.741 g of propylene glycol monomethyl ether (PGME, 118 占 폚), 20.534 g of ethyl lactate (EL, boiling point 158 占 폚) and 41.069 g of? -Butyl lactone (GBL, boiling point 205 占 폚) A positive photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 8]

A positive-type photosensitive resin composition was prepared in the same manner as in Comparative Example 7, except that the polybenzoxazole precursor (PA-2) of Synthesis Example 2 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

[Comparative Example 9]

A positive-type photosensitive resin composition was prepared in the same manner as in Comparative Example 7, except that the polybenzoxazole precursor (PA-3) of Synthesis Example 3 was used instead of 15 g of the polybenzoxazole precursor (PA-1) .

The polybenzoxazole precursor used in the photosensitive resin compositions according to Examples 1 to 27 and Comparative Examples 1 to 9 and the kind of the solvent and the content of the solvent are shown in Table 1 below.

(Unit: wt%) Polybenzoxazole precursor Solvent (based on 100 wt% solvent) Propylene glycol
Monomethyl ether ethyl
Lactate ? -butyl lactone Diphenyl
ether Methyl ethyl
Ketone dimethyl
Sulfoxid Example 1 PA-1 69 28 3 Example 2 PA-2 69 28 3 Example 3 PA-3 69 28 3 Example 4 PA-1 95 5 Example 5 PA-2 95 5 Example 6 PA-3 95 5 Example 7 PA-1 50 45 5 Example 8 PA-2 50 45 5 Example 9 PA-3 50 45 5 Example 10 PA-1 40 55 5 Example 11 PA-2 40 55 5 Example 12 PA-3 40 55 5 Example 13 PA-1 95 5 Example 14 PA-2 95 5 Example 15 PA-3 95 5 Example 16 PA-1 50 45 5 Example 17 PA-2 50 45 5 Example 18 PA-3 50 45 5 Example 19 PA-1 27 68 5 Example 20 PA-2 27 68 5 Example 21 PA-3 27 68 5 Example 22 PA-1 95 5 Example 23 PA-2 95 5 Example 24 PA-3 95 5 Example 25 PA-1 45 50 5 Example 26 PA-2 45 50 5 Example 27 PA-3 45 50 5 Comparative Example 1 PA-1 69.96 20.03 10.01 Comparative Example 2 PA-2 69.96 20.03 10.01 Comparative Example 3 PA-3 69.96 20.03 10.01 Comparative Example 4 PA-1 80 0 20 Comparative Example 5 PA-2 80 0 20 Comparative Example 6 PA-3 80 0 20 Comparative Example 7 PA-1 70 10 20 Comparative Example 8 PA-2 70 10 20 Comparative Example 9 PA-3 70 10 20

evaluation: Residual film ratio , Sensitivity and Film Shrinkage

The photosensitive resin composition prepared in Examples 1 to 27 and Comparative Examples 1 to 9 was coated on a glass substrate patterned with ITO in the same manner as in the slit coating process and the solvent was removed in a vacuum drying step, At 120 DEG C for 100 seconds to obtain a 4.15 mu m coating film. Thereafter, pattern exposure was performed using a broadband exposure apparatus, and the development proceeded. Thereafter, curing was carried out in a nitrogen gas stream at 250 캜.

The residual film ratio and sensitivity were evaluated in the exposure / development process, and the presence or absence of scum pattern was evaluated. After the curing, the shrinkage percentage of the film was evaluated. The results are shown in Table 2 below.

Exposure / Phenomenon Curing (250 ° C) Remaining film ratio (%) Sensitivity (mJ / cm ² ) Film shrinkage (%) Example 1 91 110 15 Example 2 92 105 16 Example 3 88 96 18 Example 4 84 115 16 Example 5 85 120 16 Example 6 85 124 16 Example 7 88 130 16 Example 8 88 132 16 Example 9 88 125 16 Example 10 90 120 16 Example 11 90 110 16 Example 12 91 124 16 Example 13 89 125 16 Example 14 91 136 16 Example 15 92 130 16 Example 16 90 137 16 Example 17 91 132 16 Example 18 89 132 16 Example 19 92 120 16 Example 20 96 150 16 Example 21 92 135 16 Example 22 89 110 16 Example 23 88 120 16 Example 24 87 115 16 Example 25 89 105 16 Example 26 90 108 16 Example 27 92 95 16 Comparative Example 1 68 275 16 Comparative Example 2 67 280 16 Comparative Example 3 72 265 16 Comparative Example 4 70 360 16 Comparative Example 5 73 370 16 Comparative Example 6 71 370 16 Comparative Example 7 66 240 16 Comparative Example 8 65 355 16 Comparative Example 9 68 370 16

As shown in Table 2, when the photosensitive resin compositions of Examples 1 to 27 having a solvent composition according to one embodiment were used, the sensitivity, the residual film ratio and the film shrinkage ratio were improved, but the comparison without the solvent composition according to one embodiment The photosensitive resin compositions of Examples 1 to 9 exhibit poor coating properties, and the residual film ratio and sensitivity are greatly degraded.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (10)

(A) an alkali-soluble resin;
(B) a photosensitive diazoquinone compound;
(C) a phenol compound;
(D) a thermal acid generator; And
(E) a solvent,
Wherein the solvent comprises an organic solvent having a boiling point of at least 100 ° C and less than 160 ° C at atmospheric pressure and an organic solvent having a boiling point of 160 ° C or more and 189 ° C or less,
The organic solvent having a boiling point of 100 ° C or more and less than 160 ° C is contained in an amount of 90% by weight or more and less than 100% by weight based on the total amount of the solvent,
Wherein the organic solvent having a boiling point of 160 캜 or more and 189 캜 or less is contained in an amount of more than 0 wt% to 10 wt% or less based on the total amount of the solvent.
The method according to claim 1,
Wherein the solvent is an organic solvent having a boiling point of at least 100 ° C and less than 160 ° C at an atmospheric pressure and an organic solvent having a boiling point of 160 ° C or more and 189 ° C or less in a ratio of 90:10 to 99.5:
The method according to claim 1,
Wherein the solvent is an organic solvent having a boiling point of at least 100 ° C and less than 160 ° C at an atmospheric pressure and an organic solvent having a boiling point of 160 ° C or more and 189 ° C or less in a ratio of 90:10 to 95: 5.
delete The method according to claim 1,
The alkali-soluble resin is a polybenzoxazole precursor, a polyimide precursor, or a combination thereof.
6. The method of claim 5,
Wherein the polybenzoxazole precursor comprises a structural unit represented by the following formula (1), and the polyimide precursor comprises a structural unit represented by the following formula (2): < EMI ID =
[Chemical Formula 1]

(2)

(In the above formulas (1) and (2)
X ¹ is a substituted or unsubstituted C6 to C30 aromatic organic group,
X ² is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic group, ,
Y ¹ is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic group- ego,
Y ² is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted quadrivalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted quadrivalent to hexavalent C3 to C30 alicyclic group- to be.)
The method according to claim 1,
The positive photosensitive resin composition
With respect to 100 parts by weight of the alkali-soluble resin (A)
5 to 100 parts by weight of the photosensitive diazoquinone compound (B);
1 to 30 parts by weight of the phenol compound (C);
(D) 1 to 50 parts by weight of a thermal acid generator; And
100 to 2000 parts by weight of the solvent (E)
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.
The method according to claim 1,
Wherein the positive photosensitive resin composition further comprises an additive selected from the group consisting of a surfactant, a leveling agent, a silane coupling agent, and a combination thereof.
A photosensitive resin film produced by using the positive photosensitive resin composition of any one of claims 1 to 3 and 5 to 8.
A display device comprising the photosensitive resin film of claim 9.